Neutral diesters of 2, 2&#39;-[isopropylidenebis (2, 6-dichloro-p-phenyleneoxy)]-diethanol



NEUTR L nmsraus or 2,2'-[I'SOPROPYLIDENE- BIS(-2,6 DICHLORO p PHENYLENEOXY)] DI.- ETHANOL Everett C. Hurdis, Clifton, and John F. Petras, Glen Rock, N.J., assignors to United States Rubber Comp'any, New York, N.Y., a corporation of New Jersey N Drawing. Application January 28, 1957 Serial No. 636,498

3 Claims. (Cl. 260-485) The invention comprises new compositions of matter, namely, the neutral diesters of 2,2'-[isopropylidenebis- (2,6-dichloro-p-phenyleneoxy) Jdiethanol, represented by the formula where R is either methyl or ethyl.

These new compounds are copolymerizable monomers and (like the unsaturated polyesters described in the Carleton Ellis US. Patent No. 2,195,362, dated March 26, 1940, and US. Patent No. 2,255,313, dated September 9, 1941) they can be copolymerized in combination with various reactive (copolymerizable) ethylenic monomers, such as vinyltoluene, vinyl acetate, 2-methyl-5- vinylpyridine, methyl methacrylate, diallyl phthalate, triallyl' cyanurate, N-vinylphthalimide, diallyl benzenephosphonate, etc., to give new and useful plastics. However, in contradistinction to the conventional unsaturated polyesters covered by the above mentioned Ellis patents, the new monomer of'this invention has a number of important advantages. styrene in mixtures containing 30-70% styrene, the following properties result (in comparison with conventional unsaturated polyesterstyrene mixtures):

(1) Higher heat distortion temperature.

. (2) Greater chemical resistance.

(3) Greater resistance to discoloration on exposure tolight.

These advantages of the new copolymerizable mono-- trier. of. this invention are the result of several important difierences in its chemicalmake-up as compared with conventional copolymerizable unsaturated polyesters:

(1) The new monomer of this invention is prepared from substantially two mols of dialkyl ester of dicarboxylic acid per mol of the dihydroxy compound, resulting in a definite chemical compound of relatively low molecular weight. The conventional unsaturated copolymerizable polyesters, i.e., those covered by the above mentioned Ellis patents, in contrast are prepared by reacting substantially only one mol of unsaturated dicarboxylic acid with one mol of the dihydroxy compound, so that there results a mixture of chemical species with a broad molecular weight distribution and relatively high average molecular Weight.

As indicated in our prior copending application Serial No. 622,548, filed November 16, 1956, 2,2'-[isopropylidenebis(2,6-dichloro-p-phenyleneoxy)] diethanol is preparable from 4,4-isopropylidenebis(2,6-dichlorophenol) by reaction with either ethylene oxide or. chlorohydrin, as illustrated by the following Example A (1) and (2) Specifically, when copolymerized with- EXAMPLE A This example demonstrates (1) preparation of 4,4-isopropylidenebis(2,6-dichlorophenol), and (2) preparation of 2,2 [isopropylidenebis(2,6-dichloro-p-phenyleneoxy] 5 diethauol therefrom.

(l) A reaction flask of 12 liters capacity, equipped with mechanical stirrer, dropping funnel and reflux condenser was. charged with the following:

4,4'-isopropyl-idenediphenol (Bisphenol A) M.P.

160 C.-162 C., 3 mols g 684 Acetic acid, glacial ml 3420 The mixture was heated to 40 C., and then 1701 g. sulfuryl chloride (12.8 mols) was added slowly through a dropping funnel, adjusting the rate of addition to keep the pot temperature below 60 C. The sulfur dioxide and hydrogen chloride evolved were disposed of by a simple scrubber. After all sulfuryl chloride was added,

Analysis Calculated Observed Hydroxyl number 306 302 Chlorine, percent 38. 8 38; 3

(2) The tetrachlorinated bisphenol' (4,4'-isopropylidenebis(2,6 dichlorophenol)) prepared as above was then reacted with ethylene oxide as follows:

A reaction flask of 2 liter capacity, equipped with-mechanical stirrer, gas inlet tube and reflux condenser was charged with:

I'sopropylidenebis(2,6-dichlorophenol), 2 mols g 732 Propylene glycol, used as solvent ml 150 Benzyltrimethylammonium chloride, aqueous solution ml 32 50% sodium hydroxide solution g 16 The charge was melted and kept at -l15 C., while ethylene oxide was bubbled in. When the mixture had gained grams in weight (theory g.) the reaction was discontinued. The reaction mixture was then dissolved in 8 liters of hot methanol, and 4 liters of water were added to precipitate the product in crystalline form. By filtering and drying, 1398 g. of material melting at 112 C.l 14 C. was obtainedi By adding an additional 2 liters of water to the mother liquor a second fraction weighing 191 g. of M.P. 109 C.ll2 C. was isolated. Total yield was 87.5%. The following analysis confirmed that the product was 2,2-[isopropylidenebis(2,6- dichloro-p-phenyleneoxy)l diethanol.

(2) The new monomers of this invention are so prepared that the unsaturation in the compounds occurs in definite, known positions at the ends of the molecular chains, rather than dispersed at random throughout the molecules as in the case of conventional copolymerizable unsaturated polyesters. Localization of the unsaturation at the chain ends in this way usually results in superior physical properties in copolymers, because of the high degree of structural regularity obtained.

(3) Conventional unsaturated polyesters have units held together by ester linkages entirely. The new copolymerizable monomers of this invention contain a considerable proportion of chemically stable phenyl ether linkages with resulting advantages in resistance to chemicals, heat and light.

The following examples are given to illustrate the invention, parts being by weight.

EXAMPLE 1 This example demonstrates the ester interchange reaction between 2,2 [isopropylidenebis(2,6 dichloro-pphenyleneoxy)]diethanol and dimethyl fumarate to produce the neutral methyl fumarate diester.

A reactor was charged with:

2,2 [isopropylidenebis(2,6 dichloro-p-phenyleneoxy)]diethanol 0.5 mol g 227 Dimethyl fumarate, 1.5 mols g 216 Toluene ml 200 p-Tert-butylcatechol ..g 0.8

Calculated Observed Molecular weight 678 840 Saponification equivale 170 186 Chlorine, percent 20. 3 21. 8

The monomer prepared in this way was copolymerized with styrene in a composition containing 50% by Weight of styrene and 4% of benzoyl peroxide paste (1:1 benzoyl peroxide and tricresyl phosphate). The product was a hard, transparent plastic. As indicated in Table I, this product showed the exceptionally high heat distortion temperature of 133 C. (compared with about 80 C. for commercial general purpose unsaturated polyester styrene mixtures). The other properties measured were comparable to or better than a conventional general purpose unsaturated polyester styrene composition.

EXAMPLE 2 This example demonstrates the preparation of a co- 4 polymerizable monomer from 2,2'- [isopropylidenebis- (2,o-dichloro-p-phenyleneoxy)ldiethanol and diethyl fumarate by ester interchange.

A reactor was charged with the following:

5 2,2 [isopropylidenebis(2,6 dichloro-p-phenyleneoxy)]diethanol, M.P. 114-117 C-., 0.625 p mol g 284 Diethyl fumarate, 2.24 mols (80% excess) g 322 Benzene ml 250 Thesmall amount of water in the system was removed azeotropically by refluxing at 100 C.-110 C. pot temperature. The mixture was then cooled to 95 C. and 4 ml. of tetrabutyl titanat'e was added. The mixture was then slowly distilled, adjusting the rate of takeoff so that vapor temperature stayed in the range 70 C.75 C. When evolution of ethyl alcohol slowed, the pot temperature was raised to a maximum of 150 C. to insure completeness of reaction. The mixture was then diluted with an equal volume of benzene plus 3 ml. of water and the titanate ester catalyst destroyed by heating 2 hours at 75 C. with stirring. After filtration from precipitated titani um dioxide, the benzene and unreacted diethyl fumarate were removed by vacuum distillation. On cooling, the

product formed an extremely viscous liquid which grad- .ually set to a glassy solid. The neutral ethyl fumarate diester obtained in this way was copolymerized with styrene in two combinations using, respectively, and 50% styrene. Products obtained were clear, hard plastics with useful properties.

The physical testing data listed in Table I indicate exceptionally high heat distortion temperature, as compared with commercial general purpose unsaturated polyester styrene mixtures. Theother physical properties obtained were comparable to or better than commercial general purpose unsaturated polyester styrene mixtures.

, TABLE 1 Properties of copolymers of styrene with neutral diesters of 2,2 [is0pr0pylidenebis(2,6 dichloro-p-phenyleneoxy) ldiethanol and monoalkyl fumarate Material 01 Example 1 V 2 2 a Cured 15 hrs. at 0. +1 hr. at 0. +1 hr. at 0 +1 hr. at 0 Physical Properties:

55 Rockwell R hardness 126 127 127 Tensile strength, p.s.i 4, 900 5, 100 5, 300 A.S.'I.M. Elongation at break, percent.-- 1. 5 1.0 1. 5 Youngs Modulus, p.s.i. X 10' at 25 0"; 510 480 490 60 C 450 440 430 75 G 410 410 100 0-. 330 290 270 60 0.- 170 87 120 0.- 5 0 3.7 4 5 Izod notched impact strength, ft. lb. per

inch of notch 0.22 0. 24 0 21 Heat distortion temperature, C 133 124 126 Norn.-Elongations were calculated from jaw separation and are 65 therefore higher than true absolute values. A jaw separation elongation of 8% corresponds to elongation of 1.31.5% by A.S.I.M.

Having thus described our invention, what we claim and desire to protect by Letters Patent is:

1. A fumaroid type compound represented by the gen- 7 eral formula w r... .n- MM where R in each instance represents -CH 3. A fumaroid compound represented by the general formula where R in each instance represents -C H References Cited in the file of this patent UNITED STATES PATENTS 2,359,622 Coleman et a1. Oct. 3, 1944 2,634,251 Kass Apr. 7, 1953 2,652,419 DeGroote Sept. 15, 1953 

1. A FUMAROID TYPE COMPOUND REPRESENTED BY THE GENERAL FORMULA 